Functional Cyclic Olefin Polymer, Process for Obtaining the Same and Compositions Containing the Same

Abstract

The present invention relates to a functional cyclic olefin polymer obtained from hydrogenation of a cyclic olefin polymer, wherein the cyclic olefin polymer comprises at least a monomeric unit A′ derived from a monomer A having a norbornene ring and a polar functional group, wherein the amount of the monomeric unit A′ is in the range of from 20% to 100% by mole, 50% to 100% by mole, from 60% to 100% by mole, or from 70% to 100% by mole, based on the total amount of the monomeric units of the cyclic olefin polymer. The present invention further relates to a process for producing the functional cyclic olefin polymer, a composition comprising the functional cyclic olefin polymer, and the use of the functional cyclic olefin polymer. The functional cyclic olefin polymer of the present invention exhibits improved properties, especially in terms of mechanical properties and barrier properties.

1 . A functional cyclic olefin polymer obtained from hydrogenation of a cyclic olefin polymer, wherein the cyclic olefin polymer comprises at least a monomeric unit A′ derived from a monomer A having a norbornene ring and a polar functional group,
 wherein the amount of the monomeric unit A′ is in the range of from 20% to 100% by mole, 50% to 100% by mole, from 60% to 100% by mole, or from 70% to 100% by mole, based on the total amount of the monomeric units of the cyclic olefin polymer. 
 
     
     
         2 . The functional cyclic olefin polymer of  claim 1 , wherein the functional cyclic olefin polymer has a polar force in the range from 0.5 to 20 mN/m. 
     
     
         3 . The functional cyclic olefin polymer of  claim 1 , wherein the polar functional group in monomer A is selected from aldehyde groups, alkylcarbonyloxy groups, arylcarbonyloxy groups, alkoxycarbonyl groups, aryloxycarbonyl groups, alkoxysilyl, aryloxysilyl, amine groups, amide groups, imide groups, hydroxy, hydroxyalkyl groups, hydroxyaryl groups, carboxyl groups, anhydride groups, halogen groups, cyano groups or a combination thereof. 
     
     
         4 . The functional cyclic olefin polymer of  claim 1 , wherein the monomer A comprises or is selected from a monomer having Formula (I), a monomer having Formula (II), a dicyclopentadiene having a polar functional group, or a combination thereof, 
       
         
           
           
               
               
           
         
       
       wherein R 1 , R 2 , R 3 , R 4 , independent from each other, represent a hydrogen atom, a polar functional group having a halogen, silicon, oxygen or nitrogen atom, or a hydrocarbon group having 1 to 20 carbon atoms, wherein at least one of R 1  and R 2  represents the polar functional group, and at least one of R 3  and R 4  represents the polar functional group. 
     
     
         5 . The functional cyclic olefin polymer of  claim 4 , wherein the polar functional group is selected from C 1 -C 20 -alkanal groups; C 6 -C 20 -aryl aldehyde groups; hydroxy-C 1 -C 20 -alkyl, hydroxy-C 6 -C 20 -aryl; imide groups; carboxyl, carboxyl-C 1 -C 20 -alkyl, carboxyl-C 6 -C 20 -aryl, and anhydride groups thereof, hydroxy; C 1 -C 20 -alkoxysilyl groups, C 6 -C 20 -aryloxysilyl; C 1 -C 20 -alkylcarbonyloxy groups; C 6 -C 20 -arylcarbonyloxy groups; C 1 -C 20 -alkoxycarbonyl groups, C 6 -C 20 -aryloxycarbonyl; halogen group; cyano; or a combination thereof. 
     
     
         6 . The functional cyclic olefin polymer of  claim 4 , wherein the polar functional group is selected from hydroxy; hydroxy C 1 -C 20 -alkyl, hydroxy-C 6 -C 20 -aryl; carboxyl, carboxyl-C 1 -C 20 -alkyl, carboxyl-C 6 -C 20 -aryl, and anhydride groups thereof, C 1 -C 20 -alkylcarbonyloxy groups; C 6 -C 20 -arylcarbonyloxy groups; C 1 -C 20 -alkoxycarbonyl groups; C 6 -C 20 -aryloxycarbonyl; or a combination thereof. 
     
     
         7 . The functional cyclic olefin polymer of  claim 4 , wherein the polar functional group is selected from hydroxy, hydroxy C 1 -C 20 -alkyl, hydroxy-C 6 -C 20 -aryl, or a combination thereof. 
     
     
         8 . The functional cyclic olefin polymer of  claim 1 , wherein the monomer A comprises or is selected from 5-norbornene-2-methanol, 5-norbornene-2,3-dicarboximide, 5-norbornene-2,3-dicarboxylic anhydride, 5-norbornene-2-carboxylic acid, 5-norbornene-2,3-dicarboxylic acid, 2,2-bis(hydroxymethyl)-5-norbornene, N-hydroxy-5-norbornene-2,3-dicarboxylic acid imide, 5-norbornene-2-carboxaldehyde, 5-norbornene-2-ol, methyl 5-norbornene-2-carboxylate, 5-norbornene-2-yl acetate, 8-methoxycarbonyl-tetracyclododecene, 8-methyl-8-methoxycarbonyl-tetracyclododecene, 8-hydroxymethyltetracyclododecene, tetracyclododecene-8,9-dicarboxylic acid, tetracyclododecene-8,9-dicarboxylic anhydride, 8-cyanotetracyclododecene, tetracyclododecene-8,9-dicarboxylic acid imide, 8-chlorotetracyclododecene, 8-trimethoxysilyl-tetracyclododecene, or a combination thereof. 
     
     
         9 . The functional cyclic olefin polymer of  claim 1 , wherein the cyclic olefin polymer further comprises a monomeric unit B′ derived from a comonomer, wherein the comonomer is selected from cyclic olefins that do not have a functional group other than olefinic double bond. 
     
     
         10 . The functional cyclic olefin polymer of  claim 1 , wherein the comonomer is selected from norbornene, norbornadiene, cyclopropene, cyclobutene, cyclopentene, methylcyclopentene, cyclohexene, methylcyclohexene, cycloheptene, cyclooctene (cis and trans), cyclopentadiene, cyclohexadiene, methylcyclohexadiene, cyclooctadiene, methylcyclooctadiene, phenylcyclooctadiene, 2-methyl-5-norbornene, 2-ethyl-5-norbornene, 2-butyl-5-norbornene, 2-hexyl-5-norbornene, dicyclopentadiene, 8-methyl-tetracyclododecene, 8-ethyltetracyclododecene, 8-cyclohexyltetracyclododecene, 8-cyclopentyl-tetracyclododecene, or a combination thereof. 
     
     
         11 . A process for producing the functional cyclic olefin polymer of  claim 1 , comprising:
 (i) polymerizing a monomer through ring-opening metathesis polymerization in the presence of a catalyst, to form a cyclic olefin polymer, wherein the monomer comprises at least a monomer A having a norbornene ring and a polar functional group; and   (ii) hydrogenating the cyclic olefin polymer.   
     
     
         12 . The process of  claim 11 , wherein step (i) is carried out in a solvent selected from dichloromethane, tetrahydrofuran, dimethylformamide, toluene, or xylene. 
     
     
         13 . The process of  claim 12 , wherein in step (i), the concentration of the monomer added for the polymerization is in the range from 0.01 mol/L to 5 mol/L. 
     
     
         14 . The process of  claim 11 , wherein the catalyst in step (i) is an orgaoruthenium compound having formula of; 
       
         
           
           
               
               
           
         
       
       or the catalyst in step (i) is Grubbs 2nd catalyst. 
     
     
         15 . The process of  claim 11 , wherein a vinyl compound is further added at the end of step (i. 
     
     
         16 . The process of  claim 11 , wherein step (ii) is carried out by adding a hydrogenation agent or adding a hydrogenation catalyst and hydrogen to hydrogenate the carbon-carbon double bonds in the cyclic olefin polymer obtained from step (i). 
     
     
         17 . The process of  claim 16 , wherein the hydrogenation agent is added in an amount such that the mole ratio of the hydrogenation agent to unsaturated double bond in the cyclic olefin polymer obtained from step (i) is in the range from 1 to 20 (mol/mol). 
     
     
         18 . The process of  claim 16 , wherein trialkyl amine is further added in step (ii) when step (ii) is carried out by adding a hydrogenation agent, in the same molar amount as the hydrogenation agent, preferably the trialkyl amine is trimethylamine, triethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, triheptylamine, trioctylamine, or a combination thereof. 
     
     
         19 . The process of any one of  claim 11 , wherein the monomer further comprises a comonomer selected from norbornene, norbornadiene, cyclopropene, cyclobutene, cyclopentene, methylcyclopentene, cyclohexene, methylcyclohexene, cycloheptene, cyclooctene (cis and trans), cyclopentadiene, cyclohexadiene, methylcyclohexadiene, cyclooctadiene, methylcyclooctadiene, phenylcyclooctadiene, 2-methyl-5-norbornene, 2-ethyl-5-norbornene, 2-butyl-5-norbornene, 2-hexyl-5-norbornene, dicyclopentadiene, 8-methyl-tetracyclododecene, 8-ethyltetracyclododecene, 8-cyclohexyltetracyclododecene, 8-cyclopentyl-tetracyclododecene, or a combination thereof. 
     
     
         20 . (canceled) 
     
     
         21 . A composition, comprising a functional cyclic olefin polymer obtained from hydrogenation of a cyclic olefin polymer, wherein the cyclic olefin polymer comprises at least a monomeric unit A′ derived from a monomer A having a norbornene ring and a polar functional group, wherein the polar functional group is selected from hydroxy, hydroxyalkyl group, hydroxyaryl group, carboxyl, alkylcarbonyloxy, arylcarbonyloxy, aryloxycarbonyl, alkoxycarbonyl such as —COOCH 3 , or a combination thereof, wherein the amount of the monomeric unit A′ is in the range from 20% to 100% by mole, 50% to 100% by mole, from 60% to 100% by mole, or from 70% to 100% by mole, based on the total amount of the monomeric units of the cyclic olefin polymer. 
     
     
         22 . A composition, comprising a functional cyclic olefin polymer obtained from hydrogenation of a cyclic olefin polymer, wherein the cyclic olefin polymer comprises at least a monomeric unit A′ derived from a monomer A, wherein monomer A comprises or is selected from a monomer having Formula (I), a monomer having Formula (II), a dicyclopentadiene having a polar functional group, or a combination thereof, 
       
         
           
           
               
               
           
         
         wherein R 1 , R 2 , R 3 , R 4 , independent from each other, represent a polar functional group, a hydrogen atom, or a hydrocarbon group having 1 to 20 carbon atoms, wherein at least one of R 1  and R 2  represents the polar functional group, and at least one of R 3  and R 4  represents the polar functional group, 
         wherein the polar functional group is independently selected from C 1 -C 20 -alkanal groups; C 6 -C 20 -aryl aldehyde groups; hydroxy-C 1 -C 20 -alkyl, hydroxy-C 6 -C 20 -aryl; imide groups; carboxyl, carboxyl-C 1 -C 20 -alkyl, carboxyl-C 6 -C 20 -aryl, and anhydride groups thereof, hydroxy; C 1 -C 20 -alkoxysilyl groups; C 6 -C 20 -aryloxysilyl; C 1 -C 20 -alkylcarbonyloxy groups; C 6 -C 20 -arylcarbonyloxy groups; C 1 -C 20 -alkoxycarbonyl groups; C 6 -C 20 -aryloxycarbonyl; halogen group; cyano; or a combination thereof, 
         wherein the amount of the monomeric unit A′ is in the range from 20% to 100% by mole, 50% to 100% by mole, from 60% to 100% by mole, or from 70% to 100% by mole, based on the total amount of the monomeric units of the cyclic olefin polymer. 
       
     
     
         23 .- 26 . (canceled) 
     
     
         27 . A barrier composition comprising a functional cyclic olefin polymer obtained from hydrogenation of a cyclic olefin polymer, wherein the cyclic olefin polymer comprises at least a monomeric unit A′ derived from monomer A, wherein the monomer A comprises or is selected from a monomer having Formula (I), a monomer having Formula (II), a dicyclopentadiene having a polar functional group, or a combination thereof, 
       
         
           
           
               
               
           
         
         wherein R 1 , R 2 , R 3 , R 4 , independent from each other, represent a polar functional group, a hydrogen atom, or a hydrocarbon group having 1 to 20 carbon atoms, such as 2, 3, 4, 5, 6, 7, 8, 9, 10, 12, 15, 16 and 18 carbon atoms, wherein at least one of R 1  and R 2  represents the polar functional group, and at least one of R 3  and R 4  represents the polar functional group, 
         wherein the polar functional group is independently selected from hydroxy, hydroxy-C 1 -C 20 -alkyl, hydroxy-C 6 -C 20 -aryl, or a combination thereof, wherein the amount of the monomeric unit A′ is in the range from 20 to 100% by mole, 50 to 100% by mole, from 60 to 100% by mole, or from 70 to 100% by mole, based on the total amount of the monomeric units of the cyclic olefin polymer. 
       
     
     
         28 . (canceled)